US9447246B2 - Method of covalently bonding an organic metal complex to a polymer - Google Patents

Method of covalently bonding an organic metal complex to a polymer Download PDF

Info

Publication number
US9447246B2
US9447246B2 US14/131,622 US201214131622A US9447246B2 US 9447246 B2 US9447246 B2 US 9447246B2 US 201214131622 A US201214131622 A US 201214131622A US 9447246 B2 US9447246 B2 US 9447246B2
Authority
US
United States
Prior art keywords
metal complex
reactant
polymer
organic
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
US14/131,622
Other languages
English (en)
Other versions
US20140142259A1 (en
Inventor
Daniel Volz
Tobias Grab
Thomas Baumann
Michael Bächle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Samsung Display Co Ltd
Original Assignee
Cynora GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cynora GmbH filed Critical Cynora GmbH
Assigned to CYNORA GMBH reassignment CYNORA GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BACHLE, MICHAEL, BAUMANN, THOMAS, Volz, Daniel, GRAB, TOBIAS
Publication of US20140142259A1 publication Critical patent/US20140142259A1/en
Application granted granted Critical
Publication of US9447246B2 publication Critical patent/US9447246B2/en
Assigned to SAMSUNG DISPLAY CO., LTD. reassignment SAMSUNG DISPLAY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CYNORA GMBH
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/26—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/14—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing two or more elements other than carbon, oxygen, nitrogen, sulfur and silicon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/08—Copper compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/58—Pyridine rings
    • C07F9/587—
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/26—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H01L51/004—
    • H01L51/009—
    • H01L51/0091—
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
    • H01L51/0043—
    • H01L51/5016—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates in particular to a method for covalently binding an organic metal complex to a polymer (a polymeric matrix).
  • the organic metal complex comprises at least one metal center and at least one organic ligand.
  • the method comprises the performance of a first reaction, which comprises a first reactant in the form of an organic metal complex and a second reactant in the form of a polymer, wherein during the reaction the metal complex is covalently bound to the polymer.
  • transition metal complexes Due to their properties, phosphorescent transition metal complexes become more and more important as highly efficient emitters in optoelectronic components such as OLEDs.
  • the spin-orbit coupling induced by the transition metal atom results in an increased intersystem-crossing rate from the excited singlet state to the triplet state and thus in the use of the singlet excitons as well as the triplet excitions for emission and thereby allows a theoretical achievable internal quantum yield of 100%.
  • phosphorescent dyes are usually introduced into appropriate energetically adjusted host materials.
  • Polymeric structures are particularly suitable for this purpose due to the ease of processing by liquid processing from solution. Ideally, these should fulfill additional functions such as the spatial separation of the dye molecules to prevent undesirable concentration quenching processes and triplet-triplet-annihilation under emission reduction, increased charge carrier injection and transport and an increased recombination probability directly on the emitter molecules.
  • the combination of suitable polymeric host structures with appropriate statistically blended emitter compounds and additionally inserted charge transport molecules represents a method diversely used for the preparation of polymeric light emitting diodes (PLEDs).
  • PLEDs polymeric light emitting diodes
  • the OLED components produced this way have mostly high efficiencies, these mixed systems can be subject to undesired phase separations, aggregations or crystallization processes, which have a negative effect on the capacity and the lifetime of the components. Therefore, the production of adapted (co)polymers, which fulfill additional functions such as charge transport and emission while at the same time using the advantages of liquid processing, is of steadily increasing interest.
  • FIG. 1 shows the general scheme for the linkage of organic metal complexes (first reactant) with a polymer (second reactant), each carrying a corresponding anchor group which enables the bonding and optionally the cross-linking of the metal complex in accordance with an embodiment of the present invention.
  • FIG. 2 shows selected examples of anchor groups of a first and a second anchor group species (each arranged in rows) in accordance with an embodiment of the present invention.
  • FIG. 3 shows a reaction for the cross-linking of an alkyne substituted copper complex with a polymeric azide as second reactant, wherein the reaction proceeds self-catalyzed in accordance with an embodiment of the present invention.
  • FIG. 4 shows a histogram of the AFM-picture before and after rinsing with xylene (see example 3) in accordance with an embodiment of the present invention.
  • FIG. 5 shows the photoluminescence spectra of the compounds 9.2 A-C (powder measurement, room temperature, under normal atmosphere) in accordance with an embodiment of the present invention.
  • the invention relates in a first aspect to a method for the connection of an organic metal complex to a polymer by the formation of covalent bonds.
  • covalent means a bond between non-metal elements (C, H, N, S, P, O, Si).
  • the organic metal complex comprises at least one metal center and at least one organic ligand, wherein the binding of the metal complex to the matrix is carried out via at least one ligand.
  • the method comprises the conduction of a first reaction, which comprises a first reactant in the form of an organic metal complex and a second reactant in the form of a polymer.
  • a first reaction which comprises a first reactant in the form of an organic metal complex and a second reactant in the form of a polymer.
  • the metal complex is covalently bound to the polymer via at least one ligand.
  • this first reaction is catalyzed by the metal complex bound to the polymer.
  • the metal complex is an educt/reactant and at the same time a catalyst.
  • the metal center of the metal complex is therefore the catalyzing agent of the reaction.
  • the metal center can be Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Sn and/or Pb, namely in atomic or ionic form, i.e. as a cationic central ion of the metal complex.
  • the metal center is Cu.
  • the first reaction is carried out as a cross-coupling reaction, such as, for example, Suzuki, Stille, Negishi, Kumada, Hiyama, and Sonogashira reaction
  • the metal center is preferably Pd, Pt, or Ni.
  • the metal complex is being covalently bound via at least one ligand to the polymer, wherein this bond can be single-sided or at least double-sided, i.e. a covalent connection of the metal complex via only one ligand to only one polymer molecule can take place or a simultaneous covalent connection of the metal complex via at least two ligands to at least two different polymer molecules can take place, resulting in a cross-linking of the metal complex in the polymer, generating a multi-dimensional network.
  • a multi-dimensional network is formed (cross-linking)
  • this can be in its simplest shape a ladder-like (two-dimensional) structure, in which two polymer molecules are linked by at least one metal complex, which forms via at least two ligands with one of the polymer molecules each at least one covalent bond.
  • two polymer molecules are linked by at least one metal complex, which forms via at least two ligands with one of the polymer molecules each at least one covalent bond.
  • three-dimensional networks are possible, which comprise metal complexes cross-linked with a variable number of polymeric molecules. The cross-linked metal complex is thus immobilized in the multi-dimensional network.
  • the ligand of the metal complex comprises an anchor group of a first anchor group species, which serves for the covalent binding of the metal complex via the ligand to the polymer.
  • the second reactant comprises at least one anchor group of a second anchor group species, which is suitable for the binding of the second reactant to the anchor group of the ligand of the metal complex.
  • the binding of the metal complex to the polymer results from the reaction of the anchor groups of the ligands of the metal complex with a second anchor group of a second reactant.
  • a third reactant which can also be named “spacer” molecule, takes part in the first reaction.
  • the ligand of the metal complex comprises an anchor group of a first anchor group species, which is suitable for the covalent integration of the metal complex via the ligand into the matrix by a second anchor group.
  • the second reactant comprises an anchor group of a first anchor group species, which serves for the binding of the second reactant to a second anchor group, so that the metal complex cannot bind directly to the second reactant.
  • a third reactant is added, which comprises two anchor groups of a second anchor group species, wherein each of these anchor groups of the third reactant can form a covalent bond with one first anchor group each (namely of the metal complex and of the second reactant).
  • the binding of the metal complex to the polymer takes place via the ligand by reaction of the anchor group of the ligand of the metal complex and by reaction of the anchor group of the second reactant with the same third reactant, so that a binding of the metal complex to the polymer results.
  • the metal complex comprises at least two anchor groups of a first anchor group species, which serve for the covalent binding of the metal complex via the ligands to the polymer.
  • the second reactant comprises at least one anchor group of a second anchor group species, which is suitable for the binding of the second reactant to a first anchor group of the ligand of the metal complex.
  • the binding of the metal complex to the polymer results from the reaction of the at least two anchor groups of the metal complex with one second anchor group each of a second reactant.
  • a third reactant takes part as “spacer” molecule in the first reaction.
  • the ligand of the metal complex comprises at least two anchor groups of a first anchor group species, which is suitable for the covalent integration of the metal complex via the ligand into the matrix via a second anchor group.
  • the second reactant comprises an anchor group of a first anchor group species, which serves for the binding of the second reactant to a second anchor group, so that the metal complex cannot directly bind to the second reactant.
  • a third reactant is added, which comprises two anchor groups of a second anchor group species, wherein each of these anchor groups of the third reactant can form a covalent bond with one first anchor group each (namely of the metal complex and of the second reactant).
  • the binding of the metal complex into the multidimensional network takes place via the ligand by reaction of the anchor group of the ligand of the metal complex and by reaction of the anchor group of the second reactant with the same third reactant, so that a cross-linking of the metal complex results.
  • the third reactant (“spacer” molecule) can be, for example, an alkyl chain of a desired chain length that comprises at two molecule parts spaced apart from each other, e.g. at ends opposite to each other, one anchor group each, which mediates the binding to the metal complex or to the second reactant.
  • alkyl chains aryl, heteroaryl, alkenyl, alkinyl, trialkylsilyl and triarylsilyl groups and substituted alkyl, aryl, heteroaryl and alkenyl groups, optionally with substituents such as halogens, lower alkyl groups and/or electron donating and withdrawing groups, as well as common charge transport units such as, for example, arylamines, carbazoles, benzimidazoles, oxadiazoles etc. are also possible.
  • the substituents can also lead to annulated ring systems.
  • the metal complex and the second reactant are soluble in a common organic solvent (in particular for the production of OLED components).
  • common organic solvents include ethers, alkanes as well as halogenated aliphatic and aromatic hydrocarbons and alkylated aromatic hydrocarbons, especially toluene, chlorobenzene, dichlorobenzene, mesitylene, xylene and tetrahydrofuran.
  • the formed multi-dimensional network with cross-linked organic metal complexes is insoluble, which in particular makes the formation of a structure of several overlapping layers of such a multi-dimensional network possible in a simple manner.
  • the first and the second anchor group may in particular be selected from the group of chemical groups shown in FIG. 2 . If the metal complex is an emitter, the anchor group is preferably not conjugated to the emitter system in order not to affect the emission of the complex.
  • any organic transition metal complex which carries at at least one of its organic ligands a first anchor group, can be used in the method.
  • the metal complex comprises at least one metal center and at least one ligand.
  • the metal complex can be mononuclear or polynuclear (di-, tri-, tetranuclear, etc.) and can carry one or several ligands.
  • the ligands can be mono- or polydentate. If a mononuclear complex carries only one ligand, this ligand is polydentate. If the complex is not neutral, a corresponding counter ion has to be provided, which preferably does not take part in the first reaction as described herein.
  • the ligands at the metal center are not exchanged or replaced by other ligands.
  • the occurring reaction takes place exclusively directly at the ligand or in the ligand sphere, the basic structure of the metal complex remains unchanged.
  • the occurring reaction constitutes a covalent linkage, wherein the resulting new covalent bonds are preferably formed between non-metal elements.
  • Preferred organic metal complexes are, for example, light emitters, which can be applied in optoelectronic components, such as OLEDS.
  • Another group of preferred metal complexes are semiconductors. Such emitting and semiconducting metal complexes are known in the state of art.
  • the number of anchor groups at a metal complex is depending on whether the metal complex shall be bound in a single-sided or in an at least double-sided manner to a polymer.
  • the metal complex For a single-sided binding of a metal complex to a polymer, the metal complex comprises one anchor group.
  • At least one ligand of the metal complex comprises a first anchor group.
  • a metal complex comprises at least two anchor groups, preferably of one anchor group species, which can be arranged at one ligand or are preferably distributed to two ligands of the metal complex.
  • several ligands of a metal complex comprise one or several anchor groups, wherein the number of anchor groups at the metal complex and at the second ligand determines the degree of cross-linking.
  • the multi-dimensional network formed in a preferred embodiment of the method by binding of a metal complex to more than one polymer (at least double-sided binding) is a two-dimensional or three-dimensional network.
  • a three-dimensional network is preferred.
  • the second reactant used in the method can be selected from a group consisting of a monomer, a oligomer and a polymer.
  • Low-molecular, reactive molecules are here referred to as monomers, which can react to molecular chains or networks, to unbranched or branched polymers. Examples are common monomers such as styrene, ethylene, propylene, vinylchloride, tetrafluoro ethylene, acrylic acid methylester, methacrylic acid methylester, bisphenol A/phosgene, ethylene glycols, terephthalic acids and organochloro silanes.
  • a molecule which is composed of 2 to 30 structurally identical or similar units is referred to as oligomer herein.
  • oligomers are oligoethylene, oligopropylene, oligovinylchloride, oligotetrafluoro ethylene, oligoacrylic acid methylester, oligomethacrylic acid methylester, oligocarbonates, oligoethylene glycol, oligoethylene terephthalate, oligo(organo)siloxanes.
  • Polymers are molecules which are composed of at least 10, preferably at least 15, more preferably at least 20 and most preferably of at least 30 structural identical or similar units.
  • polymers examples include polystyrene, polyethylene, polypropylene, polyvinylchloride, polytetrafluoro ethylene, polyacrylic acid methylester, polymethacrylic acid methylester, polycarbonates, polyethylene glycol, polyethylene terephthalate, and poly(organo)siloxanes.
  • cross-linking is only known between polymers, which are bound to metal complexes, wherein the polymers always react in a cross-linking reaction to themselves, thus are only homo-cross-linked.
  • cross-linking is initiated by the formation of a bond at the ligands of the metal complex, whereby the corresponding polymers are hetero-cross-linked with the metal complex.
  • the invention relates in one embodiment to materials, in particular to liquid-processable optoelectronic materials, which ensure due to their special structure both the covalent binding of a metal complex, for example a highly efficient emitter metal complex, to a functionalized second reactant in the form of a polymer, and optionally their cross-linking which leads to insolubility.
  • a metal complex for example a highly efficient emitter metal complex
  • a fourth reactant is used in the first reaction of the method besides the metal complex, the second reactant and optionally the third reactant, wherein the fourth reactant concerns a hole or electron conducting chemical group and/or a charge blocking chemical group, which can also be cross-linked as a charge transport unit or a charge blocking unit.
  • Examples for hole or electron conducting chemical groups are arylamines such as N,N′-bis(naphthalene-1-yl)-N,N′-bis(phenyl)-benzidine, N,N′-bis(naphthalene-1-yl)-N,N′-bis(phenyl)-2,2′-dimethylbenzidine, carbazoles such as 4,4-bis(carbazole-9-yl)biphenyl, 1,3-bis(carbazole-9-yl)benzene, benzimidazoles such as 1,3,5-tris(1-phenyl-1H-benzo[d]imidazole-2-yl)benzene, oxadiazoles such as 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, triazoles such as 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-
  • the fourth reactant also comprises at least one anchor group of the first and/or the second anchor group species for the connection to the polymer and/or the metal complex, depending whether the fourth reactant shall be bound to the metal complex or to the second reactant.
  • Energetically favored reactions referred to in the art as “click chemistry”, which proceed specifically and result in a single product (H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem. Int. Ed. 2001, 40, 2004-2021), can be used particularly for the first reaction.
  • the “click chemistry” comprises reactions, which are performable with high yields, are applicable in a broad range of applications, proceed (stereo)specifically, comprise simple reactions conditions (preferably insensitive to water and oxygen), comprise easily removable, as nonhazardous as possible side products and reagents (if at all), proceed in environmentally friendly and/or easily removable solvents such as water or without solvents and/or need a simple purification (extraction, phase separation, distillation or crystallization—preferably no chromatography) or no purification at all.
  • “Click” reactions are in most cases highly thermodynamically favored with often more than 20 kcal mol ⁇ 1 , leading to a single product with fast conversions and high selectivity. In most cases, carbon heteroatom bonds are formed with click reactions.
  • nucleophilic substitutions especially ring opening of tense electrophilic heterocycles such as epoxides and aziridines, carbonyl chemistry of the “non-aldol” type such as the formation of aromatic heterocycles or hydrazones, additions to carbon-carbon double bonds such as the oxidative formation of epoxides and azriridines, dihydroxylation and Michael additions as well as cycloadditions to unsaturated C—C bonds, in particular 1,3-dipolar cycloadditions and Diels-Alder reactions can be applied. Further examples for such reactions are cross-coupling reactions for the formation of C—C bonds such as the Ullmann reaction, the Sonogashira reaction and the Glaser coupling. All of these reactions are known to the person skilled in the art.
  • reactions are preferred which do not need the addition of another reactant (i.e. a reactant other than the first, second and, if applicable, the third and, if applicable, the fourth reactant), i.e. reactions that need at the most a catalyst that does not interfere with any further use.
  • a reactant i.e. a reactant other than the first, second and, if applicable, the third and, if applicable, the fourth reactant
  • reactions that need at the most a catalyst that does not interfere with any further use.
  • examples for such reactions are, besides the 1,3-bipolar cycloadditions and Diels-Alder reactions mentioned above, nitrone-alkyne reactions, nitril oxide-alkyne reactions, thiol-ene reactions, thiol-yne reactions, thiol-isocyanite reactions, tetrazole-alkene reactions and other methods known as click reactions in the chemical literature.
  • the first reaction takes place in the presence of a catalyst for the catalysis of the reaction.
  • the catalyst is an educt/reactant and at the same time a catalyst.
  • the metal complex comprises the catalyst, i.e. the metal center contained in the organic metal complex serves also as a catalyst, so that a self-catalyzed binding of the metal complex to the polymer takes place.
  • the copper-catalyzed click reaction between a terminal or activated alkyne as first anchor group of a first anchor group species of a metal complex and an azide as anchor group of a second anchor group species of a polymer is shown in FIG. 3 .
  • the metal complex is a Cu(I) or a Cu(II) complex, so that the reaction takes place self-catalytically.
  • Other possible catalysts as part of a metal complex are Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Ag, Au, Zn, Cd, Hg, Sn and/or Pb.
  • the reaction between metal complex and second reactant proceeds preferably at a temperature which is higher than room temperature. At least 50° C. are preferred, particularly preferred are temperatures from 80° C. to 120° C.
  • the reaction time needed at the particular reaction temperature can be easily determined by a person skilled in the art. Usually, a reaction time of 1 minute to 60 minutes, preferably of 10 minutes to 30 minutes is to be anticipated, so that the metal complex is immobilized and thus stabilized and insoluble.
  • the thermal activation can thereby also be carried out by exposure to microwaves, whereby the reaction times can be shortened considerably to less than 1 minute.
  • an anchor group for example an alkyne linker
  • an aromatic azide is used as complementary anchor group
  • the emission colors of such emitting complexes which are based on charge transfer transitions between the metal ions and the ligands, can be influenced.
  • metal complexes with three or more ligands e.g. four, five or six ligands
  • three or more linking positions e.g. four, five or six linking positions
  • the complexes can thereby be linked to the polymers as well as connected to hole or electron conductors (fourth reactants).
  • the optical, mechanical and electrical properties of the obtained substances can thus be influenced by the particular composition of the azide mixture.
  • the method described herein leads to an insoluble product according to a preferred embodiment of the invention, it is possibly to easily arrange several stacked layers of immobilized metal complexes, without the need for using, for example, orthogonal solvents.
  • a second reaction is performed after the first reaction described above.
  • This second reaction comprises a fifth reactant in the form of an organic metal complex and a sixth reactant for the formation of a preferably insoluble multi-dimensional network, wherein the metal complex is cross-linked during the formation of a multi-dimensional network through covalent bonds.
  • aspect described for the first reaction apply here analogously.
  • the fifth reactant of the second reaction can be identical to or different from the first reactant of the first reaction.
  • the sixth reactant of the second reaction can be identical to or different from to the second reactant of the first reaction.
  • cross-linking that occurs according to a preferred embodiment of the method of the invention allows for a fast and simple disposal of any number of photoactive layers, whose solubility does not have to be adjusted to each other as in previous systems. This results in a considerable simplification of the processing, since the selection of the individual active layers does no longer have to be orthogonal to each other with regard to solubility, but can be selected almost independently from each other. This allows for the sequential disposition of any number of different layers and thereby leads to a significant increase of efficiency and durability.
  • the anchor groups of the first and the second anchor group species are present in equimolar amounts, so that all anchor groups can form covalent bonds with complementary anchor groups.
  • the invention relates to the use of a polymer obtained with the method described herein, in particular as an emitter or an absorber in an optoelectronic component.
  • an advantage of the invention is the stabilization of the geometry of the emitter metal complex by the immobilization through cross-linking.
  • the possible movement of the ligands of the metal complexes to each other is limited.
  • the complexes are fixed and stabilized.
  • the transition probabilities for non-radiative processes are reduced by rotation and twisting in contrast to “free” complexes:
  • the emission quantum yields of the emitters are increased.
  • the fixation leads to maximal utilization of the energetic gap between the ground state and the first excited state.
  • the invention also improves the efficiency of optoelectronic components: Due to the sterical hindrance of the metal complexes the overlapping integrals between states not used for emission decrease, the population of rotational and vibrational states become less likely.
  • the stability of the complexes increases due to the prevention of bond breaking and non-radiative relaxations through free mobility of the ligands of a metal emitter system. By means of the immobilization it is possible to shift the emission of a given free, i.e. not cross-linked, emitting metal complex in the direction to or into the blue spectral range.
  • the invention relates to the use of a polymer, produced according to the method described herein, with a covalently bond metal complex as an emitter or an absorber in an optoelectronic component, provided that the metal complex is a light emitter or a light absorber.
  • the invention relates to an optoelectronic component comprising an organic metal complex covalently bound to a polymer, as described herein.
  • the optoelectronic component can be an organic light-emitting diode (OLEDs), a light-emitting electrochemical cell (LEECs or LECs), OLED sensors, optical temperature sensors, organic solar cells (OSCs), organic field effect transistors, organic diodes, organic photodiodes and “down conversion” systems.
  • OLEDs organic light-emitting diode
  • LEECs or LECs light-emitting electrochemical cell
  • OLED sensors optical temperature sensors
  • organic solar cells (OSCs) organic solar cells
  • organic field effect transistors organic diodes
  • organic photodiodes organic photodiodes and “down conversion” systems.
  • the invention relates to a method for the production of a layer of an organic metal complex bound to a polymer, in particular to a thin layer with a thickness of 75 nm to 300 nm, in particular 100 nm to 250 nm, particularly for the production of an optoelectronic component.
  • the method depends on whether the metal complex is bound single-sided or at least double-sided to the polymer.
  • liquid-processing is performed with the reaction product, because the solubility of the metal complex is increased by the binding to the polymer.
  • the of the mixture of both reactants can be applied onto a solid support by all methods known in the state of art, in particular by inkjet printing, dipping, spincoating, slot-die coating or knife coating.
  • the reaction product is insoluble.
  • the further liquid-processing of the thus obtained composite material can be carried out by means of all coating and printing methods known in the state of the art, in particular by means of inkjet printing, dipping, spincoating, slot-die coating or knife coating (knife coating).
  • the method comprises at least the following steps: First, a mixture of a first reactant in the form of an organic metal complex and a second reactant in the form of a polymer in solution is prepared.
  • Common organic solvents used include besides alcohols also ethers, alkanes as well as halogenated aliphatic and aromatic hydrocarbons and alkylated aromatic hydrocarbons, in particular toluene, chlorobenzene, dichlorobenzene, mesitylene, xylene, tetrahydrofuran, phenetole and/or propiophenone.
  • the metal complex is bound single-sided to the polymer and, in a preferred embodiment as described above, is bond in a multi-sided fashion (cross-linked), wherein the reaction between the first reactant and the second reactant is catalyzed by the metal complex.
  • the formation of the single-sided or at least multi-sided connection is carried out at higher temperature, preferably between 80° C. to 120° C.
  • the invention relates to the use of a metal complex bound to a polymer as an emitter material for an optoelectronic component, in particular as optoelectronic ink.
  • the invention in a seventh aspect, relates to an organic metal complex with at least one metal center and at least one organic ligand.
  • the metal complex comprises one, preferably two, three, four or more anchor groups of a first anchor group species for the reaction with an anchor group of a second anchor group species for the single-sided or multi-sided connection, wherein the anchor group of the metal complex can form a covalent bond with the anchor group of a second reactant during the first reaction.
  • the invention relates to the use of such a metal complex for the connection and optionally cross-linking and thus immobilization of the metal complex to a second reactant, in particular in the form of a polymer, which comprises an anchor group of a second anchor group species.
  • the invention relates to the use of a polymer for increasing the solubility of a metal complex by the single-sided connection described herein.
  • the invention relates to a method for the functionalization of an organic metal complex with one, two or more anchor groups through which the metal complex is bound to a second reactant carrying a second anchor group and can optionally (in case of at least double-sided binding) be immobilized, since the anchor group(s) of a first anchor group species of the metal complex (each) react with the anchor group of a second anchor group species of the second reactant to form a covalent bond.
  • the anchor groups shown opposite to each other can, bound on the one hand to the metal complex and on the other hand to the second reactant, form a covalent bond between the reactants and thus link and, if applicable, immobilize the metal complex.
  • First and second anchor group species are addressed here as anchor A and anchor B.
  • the anchor A shown here can represent the first or the second anchor group species and the anchor B can represent the second or the first anchor group species, respectively.
  • R1-R6 can each independently be hydrogen, halogen or substituents, which are bound via oxygen (—OR*), nitrogen (—NR*2) or silicon atoms (—SiR*3) as well as alkyl (also branched or cyclic), aryl, heteroaryl, alkenyl, akinyl groups or substituted alkyl (also branched or cyclic), aryl, heteroaryl and alkenyl groups with substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), and further generally known donor and acceptor groups such as, for example, amines, carbonyls, carboxylates and their esters, and CF3 groups.
  • R1-R6 can optionally also lead to annulated ring systems;
  • R* organic group, selected from the group consisting of: hydrogen, halogen or deuterium, as well as alkyl (also branched or cyclic), aryl, heteroaryl, alkenyl, akinyl groups or substituted alkyl (also branched or cyclic), aryl, heteroaryl and alkenyl groups with substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), and further generally known donor and acceptor groups such as, for example, amines, carboxylates and their esters, and CF3 groups;
  • X halogen, OSO2Me, OSO2Tolyl, OSO2CF3.
  • the ball shown stands for polystyrene as an example for a second reactant.
  • the heights are normalized to 1, the position of the histograms on the X-axis is arbitrary, but true to scale.
  • the histograms were not arranged on top of each other, but side by side. The processing was carried out at 40° C., the scan-size of the underlying images is 1 ⁇ m2.
  • the invention is a stabilization, connection and optionally cross-linking method of metal complexes with polymers, which consist of one or more metals and one at least bidentate, or several mono- or polydentate ligands.
  • the organic metal complex and the second reactant carry complementary chemical anchors of a (first or second) anchor group species, which are covalently bound to each other in a reaction proceeding as quickly and completely. Therefore, for example, luminescent or semiconducting metal complexes can be immobilized, e.g for applications in organic electronics, in order to increase the lifetime and long-term stability of the components.
  • such reactions are preferred which do not need the addition of another reactant besides the metal complex and the second reactant, i.e. reactions that need at the most a catalyst that does not interfere with the further use.
  • examples for such reactions are 1,3-bipolar cycloadditions, Diels-Alder reactions, nitrone-alkyne reactions, nitril oxide-alkyne reactions, thiol-ene reactions, thiol-yne reactions, thiol-isocyanite reactions, tetrazole-alkene reactions and other methods known as click reactions in chemical literature.
  • reactions which are catalyzed by the metal itself contained in the metal complex, on other words a self-catalyzed connection or cross-linking.
  • One example is the copper-catalyzed click reaction between a terminal or activated alkyne and an azide. This reaction provides regioselectively and in high yields and conversions 1,4-triazoles (see FIG. 2 ).
  • Phenylacetylene (103 mg, 1.0 mmol, 1.0 eq.) and benzyl azide (133 mg, 1.0 mmol, 1.0 eq.) were dissolved in an air-tight lockable vial with a septum in 10 mL dry dichloromethane.
  • the Cu complex (catalytic or stoichiometric amounts) was added, the vial sealed and the reaction stirred at room temperature for 2 days.
  • the reaction mixture was put in 50 mL methanol and stirred for 20 min. The complex was removed by filtering and the filtrate was concentrated.
  • the Cu complex (1,341 g, 1.0 mmol, 1.0 eq.) was dissolved in an air-tight lockable vial with a septum in 10 mL dry dichloromethane and benzyl azide (466 mg, 3.5 mmol, 3.5 eq.) was added. The reaction was stirred at room temperature for 12 hours, filtered over a syringe filter and precipitated by adding dropwise into diethyl ether.
  • the Cu complex (440 mg, 0.33 mmol, 1.0 eq.) was dissolved as first reactant in an air-tight lockable vial with a septum in 10 mL dry dichloromethane and converted with poly-(vinylbenzylazide-alt-styrene) (370 mg, 1.0 mmol, 3.0 eq.).
  • the reaction was stirred at room temperature for 12 hours, whereat the product precipitated as insoluble greenish solid from the reaction solution.
  • the precipitate was withdrawn by suction, washed with 20 mL dichloromethane, 20 mL diethyl ether and 20 mL methanol and dried in high vacuum.
  • the product poly-(4-(2-(1-(4-vinylbenzyl-1H-1,2,3-triazole-4-yl)ethyl)-2-(diphenylphosphino)pyridine)-alt- styrol@ Cul was a light green solid in 66% yield (540 mg, 0.21 mmol) and represents a cross-linked metal complex. The identity of the product was clearly proven by infrared spectroscopy and elemental analysis.
  • this layer became stabilized and insoluble.
  • a knife-coating apparatus all other known printing or coating methods such as, for example, spin-coating, slot-die or ink-jet are also possible
  • this layer became stabilized and insoluble.
  • this cross-linking provides for a stabilization and fixation of the geometric structure of the metal complexes, preventing a movement of the ligands and thus a change in structure of the excited molecules and effectively inhibiting a reduction in efficiency due to non-radiative relaxation pathways.
  • the invention relates in a preferred embodiment to the production of novel optoelectronic inks as emitter materials for organic light-emitting diodes as optoelectronic component.
  • the ink is based on electroluminescent copper(I) complexes, in which diphenylphosphinepyridines, diphenylphosphinechinolines and related heterocycles are used as ligands. These bidentate ligands form polynuclear complexes with copper(I) iodide with a ligand to metal iodide ratio of 3:2.
  • these ligand systems can be substituted with alkyne chains such as 4-butyne and coupled as a copper complex (first reactant with first anchor group) in a click reaction with azides.
  • first reactant with first anchor group first reactant with first anchor group
  • second reactant low-molecular as well as polymeric azides can be converted as a second reactant so that, for example, cross-linked, copper-containing polymers can be synthesized, which combine the electroluminescent properties of the metal complexes with the advantages of the simple liquid processing of the polymers and result in robust, insoluble layers after one baking step.
  • the advantages of liquid processing of the resulting soluble metal complex polymer composite materials short composite materials
  • cross-linked insoluble layers for the realization of multi-layer arrangements result.
  • this reaction can be carried out with other ligand classes.
  • further material functions can be implemented into the ink in addition to the connection or cross-linking. Therefore, click-reactions can be used in order to link functional semiconductors (as third reactant), which have hole-transporting or electron-transporting properties, to the complexes.
  • the anchor group e.g. the alkyne linker
  • aromatic azides are used, the emission color of the complexes, which is based on charge-transfer transitions between the metal ions and the ligands, can be influenced.
  • the dimeric complexes each contain three ligands and thus three positions for connection, the complexes can in this way be bound to the polymers as well as bound to hole and electron conductors.
  • the optical, mechanical and electrical properties of the substances obtained that way can for this reason be influenced via the respective composition of the azide mixture.
  • These parameters of the ink can be optimized by robot-supported high-throughput screening methods. With the use of different metal complexes substituted with alkynes, organic light emitting diodes in different colors can be realized, and white-light OLEDS can be achieved by suitable mixture of colors of the corresponding metal complexes.
  • Emitters in particular emitters, which were synthesized via a fourth reactant for the transport or the blocking of electrical charges, which comprises an anchor group of the first or the second anchor group species
  • a fourth reactant for the transport or the blocking of electrical charges which comprises an anchor group of the first or the second anchor group species
  • Emitters can be linked with an ideal mixture of hole conductors, electron conductors, and a polymer to an optoelectronic ink.
  • the ball shown in 27 stands for polystyrene, but can also represent any other polymer as second reactant.
  • PyrPHOS complex PyrPHOS
  • polymeric azides with a polystyrene or polyethylene glycol backbone a single-sided connection is formed by reaction via only one anchor group of the metal complex.
  • the yellow emission color of the copper-PyrPHOS complexes is influenced neither by variation of the charge transport or blocking units nor by the connection to the polymers.
  • the emission maximum of the PyrPHOS-systems lies at 550 nm.
  • thin layers can be produced by means of a wedge-shaped coating knife.
  • the substance is applied in solution onto a substrate and evenly distributed by means of a slide, which can be controlled with a definite gap width and drawing speed.
  • the films thus produced are dried by heating and a nitrogen flow, so that extremely smooth, defined layers can be produced.
  • the polymer dissolved in xylene was mixed in a vial with the metal complex solved in dichloromethane and shortly after mixing was applied as a light cloudy solution to a substrate coated with indium tin oxide (ITO) and PEDOT:PSS. An equimolar stoichiometry was chosen.
  • ITO indium tin oxide
  • PEDOT:PSS PEDOT:PSS
  • the reaction, coating and drying were carried out at various temperatures. Since the whole process was finished after a very short period of time, the samples were subsequently tempered on a heating plate at 100° C. for one hour in order to reach a high yield of the Huisgen reaction. The samples were examined under a UV-lamp as well as by atomic force microscopy. Furthermore, the films were rinsed by immersion in xylene before and after drying for monitoring the reaction. While the cross-linked product is insoluble, the reactants dissolve in this solvent, so that by the resistance of the layers a conclusion about a successful cross-linking can be drawn.
  • the roughness is very low for the measured samples with values between 0.53 and 1.64 nm, indicating an excellent morphology of the measured samples.
  • the insoluble, cross-linked PyrPHOS polymers could represent a solid-phase catalyst with immobilized Cu(I).
  • the properties of the metal complexes can be modified with such reactions, e.g.:
  • reaction shown above proceeded with complete conversion (determined with IGC-MS). Furthermore, the catalyst that is insoluble in toluene could be filtered out together with the potassium carbonate and remained intact (preservation of the yellow photoluminescence).
  • the product shown on the right side luminesced like the reactant shown on the left.
  • the typical odor of a free thiol was lacking after the reaction.
  • charge transport units as used, for example, for organic light emitting diodes can be incorporated by the linking reaction.
  • the basic structure in this figure is already known (Inorg. Chem. 2011, 50, 8293).
  • substitution with one or more anchor groups a new structure is formed, which is cross-linkable or linkable.
  • All anchor groups R can be attached to one of the ligands A or B or the anchor groups can also be distributed to both ligands.
  • the cross-linking can be influenced by the number of anchor groups per complex.
  • Known complexes can be modified by including anchor groups in a way that cross-linking is possible.
  • Heteroleptic and homoleptic complexes can be used.
  • Photoluminescence spectra of the compounds were recorded (powder measurement, room temperature, under normal atmosphere): see FIG. 5 .
  • Example complex 11 A Copper tetrakisacetonitrile tetrafluoroborate (example complex 11 A 1 mmol, 1 eq.) and accordingly copper tetrakisacetonitrile hexafluorophosphate (example complex 11 B, 1 mmol, 1 eq.) was provided with the bisphosphine ligands POP (1 eq., 1 mmol) and the ligand 4-but-4′-in-2-diphenylphosphinoxido-pyridine functionalized with anchor groups (1 eq, 1 mmol) in a small glass with stirring bar and septum under nitrogen. 10 mL dry dichloromethane were added and the reaction mixture stirred at room temperature for 2 hours. The volume was reduced to the half in vacuum and the target compound precipitated by adding dropwise to n-hexane. The identity of the compound was proven by 1H-NMR, 31-P-NMR, elemental analysis and infrared spectroscopy.
  • This concept can also be applied to metals other than copper. Thereby, some of the anchor groups must be adjusted, if necessary, to the chemical properties of the metal complexes to be linked. For some selected metals, such possibilities are shown in the following examples.
  • Ruthenium complexes also catalyze cycloadditions between alkynes and azides, but result in 1,5-triazoles in contrary to copper-catalyzed click reactions which result in 1,4-triazoles.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Physics & Mathematics (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US14/131,622 2011-07-08 2012-07-09 Method of covalently bonding an organic metal complex to a polymer Active US9447246B2 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
EP11173374.7 2011-07-08
EP11173374 2011-07-08
EP11173374 2011-07-08
EP11175125A EP2543685A1 (de) 2011-07-08 2011-07-22 Verfahren zur kovalenten Bindung eines Metallkomplexes an ein Polymer
EP11175125 2011-07-22
EP11175125.1 2011-07-22
PCT/EP2012/063447 WO2013007710A1 (de) 2011-07-08 2012-07-09 Verfahren zur kovalenten bindung eines organischen metallkomplexes an ein polymer

Publications (2)

Publication Number Publication Date
US20140142259A1 US20140142259A1 (en) 2014-05-22
US9447246B2 true US9447246B2 (en) 2016-09-20

Family

ID=44582278

Family Applications (2)

Application Number Title Priority Date Filing Date
US14/131,594 Active US9447245B2 (en) 2011-07-08 2012-07-09 Cross-linking and stabilization of organic metal complexes in networks
US14/131,622 Active US9447246B2 (en) 2011-07-08 2012-07-09 Method of covalently bonding an organic metal complex to a polymer

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US14/131,594 Active US9447245B2 (en) 2011-07-08 2012-07-09 Cross-linking and stabilization of organic metal complexes in networks

Country Status (6)

Country Link
US (2) US9447245B2 (ko)
EP (4) EP2543671A1 (ko)
JP (2) JP6253577B2 (ko)
KR (2) KR102014224B1 (ko)
CN (2) CN103649134B (ko)
WO (2) WO2013007710A1 (ko)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2543671A1 (de) 2011-07-08 2013-01-09 cynora GmbH Querverknüpfung und Stabilisierung von organischen Metallkomplexen in Netzwerken
DE102013106949A1 (de) * 2013-07-02 2015-01-08 Osram Opto Semiconductors Gmbh Optoelektronisches Bauelement, organische funktionelle Schicht und Verfahren zur Herstellung eines optoelektronischen Bauelements
DE112015001925B4 (de) 2014-04-24 2024-02-01 Samsung Display Co., Ltd. Verwendung eines Materials zur fälschungssicheren Markierung von Gegenständen, Stoffen oder Stoffgemischen sowie Verfahren zur fälschungssicheren Markierung
EP2937354A1 (en) * 2014-04-27 2015-10-28 Studiengesellschaft Kohle mbH N-substituted pyridiniophosphines, processes for their preparation and their use
DE102014210412A1 (de) 2014-06-03 2015-12-03 Siemens Aktiengesellschaft p-Dotierende Vernetzung organischer Lochleiter
EP2993176A1 (de) 2014-09-02 2016-03-09 cynora GmbH Metall(i)-komplexe für verbesserte leitfähigkeit
DE102015216658A1 (de) 2014-09-02 2016-03-03 Cynora Gmbh Strukturell Stabilisierte Kupfer(I)-Komplexe
WO2016037963A1 (de) 2014-09-08 2016-03-17 Cynora Gmbh Stabilisierte optisch aktive schicht und verfahren zur herstellung
WO2016037964A1 (de) 2014-09-08 2016-03-17 Cynora Gmbh Verbesserte optisch aktive schicht und verfahren zur herstellung
WO2016041802A1 (en) 2014-09-16 2016-03-24 Cynora Gmbh Light-emitting layer suitable for bright luminescence
CN110152739B (zh) * 2019-06-06 2022-04-15 山东师范大学 原位负载钯纳米颗粒的多孔有机复合物、合成方法及应用
JP7392482B2 (ja) * 2019-09-24 2023-12-06 株式会社豊田中央研究所 二酸化炭素還元触媒
WO2021075879A2 (ko) * 2019-10-15 2021-04-22 고려대학교 산학협력단 단백질 응집체 검출용 형광 프로브 화합물 및 이를 포함하는 단백질 응집체 검출용 형광 센서
CN110776532B (zh) * 2019-11-05 2022-05-17 江西理工大学 一种3-甲基吡啶四氮唑四核铜[i]配合物在刺激响应发光变色材料的应用
US11286269B1 (en) * 2020-08-27 2022-03-29 The United States Of America As Represented By The Secretary Of The Navy Synthesis of copper azido-based energetic compounds
JP7358708B2 (ja) 2022-03-10 2023-10-11 株式会社伸光製作所 プリント配線板

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0050358A2 (de) 1980-10-21 1982-04-28 Wacker-Chemie GmbH Vernetzungsmittel für Polyorganosiloxane auf Basis eines Umsetzungsproduktes von Kieselsäureester mit organischer Zinnverbindung und Verfahren zur Herstellung von Polysiloxanelastomeren
DE3337100A1 (de) 1983-10-12 1985-05-09 Dynamit Nobel Ag, 5210 Troisdorf Wasserloesliche titanacetylacetonate
EP0190998A1 (de) 1985-02-05 1986-08-13 Ciba-Geigy Ag Copolymerisierbare Dibenzalaceton-Palladiumkomplexe und deren Verwendung
US5395887A (en) * 1989-12-28 1995-03-07 Centre National De La Recherche Scientifique Process for cross-linking chlorinated (CO)polymers, cross-linkable compositions and shaped objects
WO2003072584A1 (de) 2002-02-26 2003-09-04 Celanese Ventures Gmbh Kovalent fixierte non-metallocene, verfahren zur herstellung von diesen und deren verwendung zur polymerisation von olefinen
US20040247934A1 (en) 2001-06-20 2004-12-09 Masataka Takeuchi Light emitting material and organic light-emitting device
WO2005042550A1 (de) 2003-10-30 2005-05-12 Merck Patent Gmbh Metallkomplexe mit bipodalen liganden
US20050196637A1 (en) 2003-08-28 2005-09-08 Norman Herron Phosphorescent material
US20060269779A1 (en) 2003-04-30 2006-11-30 Yoshiaki Takahashi Organic polymer light-emitting element material having gold complex structure and organic polymer light-emitting element
WO2010082924A1 (en) 2009-01-14 2010-07-22 Universal Display Corporation Cross-linkable copper phthalocyanine complexes
US7858724B2 (en) * 2003-12-29 2010-12-28 Osram Opto Semiconductors Gmbh Polymeric, phosphorescent, organically semi-conductive emitter materials based on perarylated boranes, method for their production and use thereof
WO2010149748A1 (de) 2009-06-24 2010-12-29 Hartmut Yersin Kupfer-komplexe für optoelektronische anwendungen
US20110089411A1 (en) * 2008-06-27 2011-04-21 Chuanjun Xia Cross linkable ionic compounds
WO2011067401A1 (en) 2009-12-03 2011-06-09 Westfälische Wilhelms-Universität Münster Use of luminescent ir(iii) and ru(ii) complexes
CN103534260A (zh) 2011-05-13 2014-01-22 辛诺拉有限公司 铜(i)络合物，尤其用于光电组件

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3969152B2 (ja) * 2001-06-21 2007-09-05 昭和電工株式会社 有機発光素子および発光材料
JP3890242B2 (ja) * 2002-03-26 2007-03-07 キヤノン株式会社 高分子化合物及び電界発光素子
JP2004027088A (ja) * 2002-06-27 2004-01-29 Jsr Corp 燐光発光剤およびその製造方法並びに発光性組成物
GB0219987D0 (en) * 2002-08-28 2002-10-09 Isis Innovation Intramolecular interactions in organometallics
JP4666338B2 (ja) * 2003-04-30 2011-04-06 昭和電工株式会社 金錯体構造を有する有機高分子発光素子材料および有機高分子発光素子
JP4226432B2 (ja) * 2003-10-16 2009-02-18 富士通株式会社 金属錯体含有高分子、有機ｅｌ素子及び有機ｅｌディスプレイ
MX2007012157A (es) 2005-04-01 2008-03-14 Intezyne Technologies Llc Micelas polimericas para suministro de farmacos.
US20070020620A1 (en) * 2005-07-14 2007-01-25 Finn M G Compositions and methods for coupling a plurality of compounds to a scaffold
KR20070105080A (ko) * 2006-04-25 2007-10-30 엘지전자 주식회사 적색 인광 화합물 및 이를 사용한 유기전계발광소자
EP1996938A4 (en) 2006-03-22 2009-12-09 Univ Utah Res Found IMMOBILIZED PROTEINS AND USE METHOD THEREFOR
US8236284B1 (en) * 2008-04-02 2012-08-07 University Of Central Florida Research Foundation, Inc. Multimodal, multifunctional polymer coated nanoparticles
DE102008040886A1 (de) * 2008-07-31 2010-02-04 Wacker Chemie Ag Durch Click-Reaktion vernetzbare mehrkomponentige Siliconzusammensetzungen
JP2014506725A (ja) 2011-01-23 2014-03-17 シノーラ ゲエムベーハー 可変調節可能な（ａｄａｐｔａｂｌｅ）発光色を有する光電子デバイス用金属錯体
EP2543671A1 (de) 2011-07-08 2013-01-09 cynora GmbH Querverknüpfung und Stabilisierung von organischen Metallkomplexen in Netzwerken

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0050358A2 (de) 1980-10-21 1982-04-28 Wacker-Chemie GmbH Vernetzungsmittel für Polyorganosiloxane auf Basis eines Umsetzungsproduktes von Kieselsäureester mit organischer Zinnverbindung und Verfahren zur Herstellung von Polysiloxanelastomeren
US4360654A (en) * 1980-10-21 1982-11-23 Wacker-Chemie Gmbh Reaction products of silicic acid esters and organic tin compounds
DE3337100A1 (de) 1983-10-12 1985-05-09 Dynamit Nobel Ag, 5210 Troisdorf Wasserloesliche titanacetylacetonate
US4647680A (en) * 1983-10-12 1987-03-03 Dynamit Nobel Ag Water-soluble titanium acetylacetonates
EP0190998A1 (de) 1985-02-05 1986-08-13 Ciba-Geigy Ag Copolymerisierbare Dibenzalaceton-Palladiumkomplexe und deren Verwendung
US5395887A (en) * 1989-12-28 1995-03-07 Centre National De La Recherche Scientifique Process for cross-linking chlorinated (CO)polymers, cross-linkable compositions and shaped objects
DE69021559T2 (de) 1989-12-28 1996-01-18 Centre Nat Rech Scient Verfahren zum vernetzen von chlorierten (co)polymeren, vernetzbare zusammensetzungen und daraus hergestellte geformte gegenstände.
US20040247934A1 (en) 2001-06-20 2004-12-09 Masataka Takeuchi Light emitting material and organic light-emitting device
WO2003072584A1 (de) 2002-02-26 2003-09-04 Celanese Ventures Gmbh Kovalent fixierte non-metallocene, verfahren zur herstellung von diesen und deren verwendung zur polymerisation von olefinen
US20060269779A1 (en) 2003-04-30 2006-11-30 Yoshiaki Takahashi Organic polymer light-emitting element material having gold complex structure and organic polymer light-emitting element
US20050196637A1 (en) 2003-08-28 2005-09-08 Norman Herron Phosphorescent material
WO2005042550A1 (de) 2003-10-30 2005-05-12 Merck Patent Gmbh Metallkomplexe mit bipodalen liganden
US7858724B2 (en) * 2003-12-29 2010-12-28 Osram Opto Semiconductors Gmbh Polymeric, phosphorescent, organically semi-conductive emitter materials based on perarylated boranes, method for their production and use thereof
US20110089411A1 (en) * 2008-06-27 2011-04-21 Chuanjun Xia Cross linkable ionic compounds
WO2010082924A1 (en) 2009-01-14 2010-07-22 Universal Display Corporation Cross-linkable copper phthalocyanine complexes
US20120267612A1 (en) * 2009-01-14 2012-10-25 Universal Display Corporation Cross-linkable copper phthalocyanine complexes
WO2010149748A1 (de) 2009-06-24 2010-12-29 Hartmut Yersin Kupfer-komplexe für optoelektronische anwendungen
WO2011067401A1 (en) 2009-12-03 2011-06-09 Westfälische Wilhelms-Universität Münster Use of luminescent ir(iii) and ru(ii) complexes
CN103534260A (zh) 2011-05-13 2014-01-22 辛诺拉有限公司 铜(i)络合物，尤其用于光电组件

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
B. Ma et al., "Multifunctional Crosslinkable Iridium Complexes as Hole Transporting/Electron Blocking and Emitting Materials for Solution-Processed Multilayer Organic Light-Emitting Diodes," Advanced Functional Materials, Apr. 2009, pp. 1024-1031, vol. 19, No. 7.
D. Liu et al., "Triazole-Based Monophosphines for Suzuki-Miyaura Coupling and Amination Reactions of Aryl Chlorides," ACS Publications, 2005, p. 4907-4910.
D. Volz et al., "Auto-Catalysed Crosslinking for Next-Generation OLED-Design," Journal of Materials Chemistry, Sep. 2012, pp. 20786-20790, vol. 22, No. 38.
D. Zink et al., Experimental and Theoretical Study of Novel Luminescent Di-, Tri-, and Tetranuclear Copper Triazole Complexes, ACS Publications, 2011, p. 3275-3283.
International Search Report and Written Opinion of International Searching Authority for PCT/EP2012/063447 dated Oct. 19, 2012.
L.I. Goryunov et al., "Reaction of Chloropentafluorobenzene and 2,3- and 2,6-Difluoro-bromobenzenes with Lithium Dimethylphosphide," Russian Journal of Organic Chemistry, vol. 45, No. 12, 2009, p. 1859-1861.
M.P. Garcia Armada et al., "Electrochemical and Bioelectrocatalytical Properties of Novel Block-Copolymers Containing Interacting Ferrocenyl Units," Journal of Organometallic Chemistry, 2008, pp. 2803-2811, vol. 693, No. 16.
N. Holten-Andersen et al., "pH-Induced Metal-Ligand Cross-Links Inspired by Mussel Yield Self-Healing Polymer Networks with Near-Covalent Elastic Moduli," Proceedings of the National Academy of Sciences (PNAS), Feb. 2011, pp. 2651-2655, vol. 108, No. 7.
Riedl/Janiak, "Anorganische Chemie," XP-002666355, 2007, p. 306.

Also Published As

Publication number Publication date
EP2543685A1 (de) 2013-01-09
EP2729506B1 (de) 2016-08-10
KR20140061390A (ko) 2014-05-21
WO2013007709A2 (de) 2013-01-17
US9447245B2 (en) 2016-09-20
JP6072026B2 (ja) 2017-02-01
CN103649133A (zh) 2014-03-19
CN103649133B (zh) 2016-07-06
JP6253577B2 (ja) 2017-12-27
EP2729505A2 (de) 2014-05-14
JP2014531472A (ja) 2014-11-27
EP2543671A1 (de) 2013-01-09
JP2014529577A (ja) 2014-11-13
EP2729506A1 (de) 2014-05-14
KR102014223B1 (ko) 2019-08-26
EP2729505B1 (de) 2016-03-23
WO2013007710A1 (de) 2013-01-17
CN103649134A (zh) 2014-03-19
KR20140061389A (ko) 2014-05-21
KR102014224B1 (ko) 2019-08-26
US20140142258A1 (en) 2014-05-22
WO2013007709A3 (de) 2013-04-04
CN103649134B (zh) 2016-07-06
US20140142259A1 (en) 2014-05-22

Similar Documents

Publication Publication Date Title
US9447246B2 (en) Method of covalently bonding an organic metal complex to a polymer
US11189806B2 (en) Heteroleptic carbene complexes and the use thereof in organic electronics
Albrecht et al. Dendritic structure having a potential gradient: new synthesis and properties of carbazole dendrimers
Wild et al. Advances in the field of π-conjugated 2, 2′: 6′, 2 ″-terpyridines
Fink et al. Synthesis and application of dimeric 1, 3, 5-triazine ethers as hole-blocking materials in electroluminescent devices
CN101134744B (zh) 杂环的化合物,其用途、有机半导体材料和电子或光电元件
Winter et al. Self‐assembly of π‐conjugated bis (terpyridine) ligands with zinc (II) ions: new metallosupramolecular materials for optoelectronic applications
US11367848B2 (en) Light-emitting layer suitable for bright luminescence
JP2010517253A (ja) ポリマー状アニオン／カチオン
US20110309304A1 (en) Luminescent silver complex
Liu et al. Effect of acetylenic chain length on the tuning of functional properties in fluorene-bridged polymetallaynes and their molecular model compounds
TW201718613A (zh) 金屬錯合物
Efrem et al. Direct arylation polymerization toward a narrow bandgap donor–acceptor conjugated polymer of alternating 5, 6‐difluoro‐2, 1, 3‐benzothiadiazole and alkyl‐quarternarythiophene: From synthesis, optoelectronic properties to devices
JP2019206676A (ja) 高分子化合物、高分子化合物の製造方法、及び、その利用
Ho et al. Synthesis, characterization and photophysical properties of metallopolyynes and metallodiynes of platinum (II) with dibenzothiophene derivatives
Reeves et al. Synthesis and investigation of cobalt chalcogenide clusters with thienyl phosphine ligands as new acceptor materials for P3HT
JP7363214B2 (ja) イオン性化合物、有機エレクトロニクス材料、インク組成物、及び有機エレクトロニクス素子
KR20200019137A (ko) 유기 일렉트로닉스 재료 및 유기 일렉트로닉스 소자
Crossley Directed CH Borylation for the Synthesis of Fused and Ladder Type Conjugated Oligomers and Polymers
KR20190111977A (ko) 분지 폴리머의 제조 방법, 분지 폴리머 및 유기 일렉트로닉스 소자
Lee et al. Synthesis and Characterization of a Tetrathiafulvalene-Based Polymer
Liu Redox-active inorganic cages and π-conjugation: covalent and non-covalent control of electronic coupling for chemical sensing, molecular switching, charge transport, and electrocatalysis
TW201329130A (zh) 包括鏻鹽基團的陽離子聚合物

Legal Events

Date Code Title Description
AS Assignment

Owner name: CYNORA GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:VOLZ, DANIEL;GRAB, TOBIAS;BAUMANN, THOMAS;AND OTHERS;SIGNING DATES FROM 20131218 TO 20131219;REEL/FRAME:031920/0725

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2551); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

Year of fee payment: 4

AS Assignment

Owner name: SAMSUNG DISPLAY CO., LTD., KOREA, REPUBLIC OF

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CYNORA GMBH;REEL/FRAME:060329/0712

Effective date: 20220527

FEPP Fee payment procedure

Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8